Acetic Acid → Ethyl 2-Formyl-2-(2-formylamino-4-thiazolyl)acetate

HRID 4935

Reaktionsgleichung

Reaktionsgleichung von HRID 4935
[H-].[Na+].[NH2:3][C:4]1[S:5][CH:6]=[C:7]([CH2:9][C:10]([O:12][CH2:13][CH3:14])=[O:11])[N:8]=1.[CH:15](OCC)=[O:16].[C:20](O)(=[O:22])C>CCCCCC.O1CCCC1>[CH:15]([CH:9]([C:7]1[N:8]=[C:4]([NH:3][CH:20]=[O:22])[S:5][CH:6]=1)[C:10]([O:12][CH2:13][CH3:14])=[O:11])=[O:16]

Komponenten

7

Edukt 4

HCID 176Acetic AcidHCID 8025Ethyl formateHCID 24758Sodium hydrideHCID 1044544-Thiazoleacetic acid, 2-amino-, ethyl ester

Produkt 1

HCID 13309500Ethyl 2-Formyl-2-(2-formylamino-4-thiazolyl)acetate

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 8028TetrahydrofuranLösungsmittel2×HCID 8058HexaneLösungsmittel

Versuchsvorschrift

Under nitrogen, 14 g (0.29 mmol) of 50% NaH in oil was washed with 2×40 ml of hexane and then suspended in 90 ml of anhydrous tetrahydrofuran (THF). To this slurry at 0° C. was added dropwise a solution of ethyl 2-(2-amino-4-thiazolyl)acetate (27 g, 0.145 mmol) in 290 ml of anhydrous THF, followed by ethyl formate (21.5 g, 0.29 mmol), and the mixture stirred at room temperature for 18 hours. The pH of reaction mixture was adjusted to 7 by the addition of 50% aqueous acetic acid and the mixture extracted with 250 ml ethyl acetate. The aqueous layer was further extracted with 2×50 ml of 1:1 THF:ethyl acetate. The extracts were combined, dried over Na2SO4 and evaporated to a solid, which was recrystallized from ethyl acetate to yield purified title product, 17.8 g (50.7%); m.p. 179°-180° C.; 1H-nmr (CDCl3 -d6 -DMSO) 1.33 (t, 3H), 4.16 (q, 2H), 7.50 (s, 1H), 8.00 (s, 1H), 8.53 (s, 1H).

Aufarbeitung

  1. customThe pH of reaction mixture
  2. extractionthe mixture extracted with 250 ml ethyl acetate
  3. extractionThe aqueous layer was further extracted with 2×50 ml of 1:1 THF
  4. dry with materialdried over Na2SO4
  5. customevaporated to a solid, which
  6. customwas recrystallized from ethyl acetate
  7. customto yield
  8. custompurified title product, 17.8 g (50.7%)

Quellen und Nachweise

ORD-Eintrag
ord-d6f8a145407c4859b6e938637fa82e5b
Quelldatensatz
uspto-grants-1993_09
Patentnummer
US05242913

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